KR101736920B1 - Aryl-substituted anthracene compound, preparation method thereof, and organic thin film transistor comprising the same - Google Patents

Aryl-substituted anthracene compound, preparation method thereof, and organic thin film transistor comprising the same Download PDF

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KR101736920B1
KR101736920B1 KR1020090125102A KR20090125102A KR101736920B1 KR 101736920 B1 KR101736920 B1 KR 101736920B1 KR 1020090125102 A KR1020090125102 A KR 1020090125102A KR 20090125102 A KR20090125102 A KR 20090125102A KR 101736920 B1 KR101736920 B1 KR 101736920B1
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송인범
조남성
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엘지디스플레이 주식회사
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Abstract

The present invention relates to an anthracene compound substituted with an aryl group, a process for producing the same, and an organic thin film transistor using the same. The compound according to the present invention is excellent in crystallinity and thin film characteristics compared with the conventional n- or p-type organic semiconductor material, and thus can form a large-area thin film by a solution process at room temperature and can reduce a leakage current, The electrical characteristics of the transistor can be improved.
Heteroatom, aromatic, fluoroaryl group, organic semiconductor, organic thin film transistor, carrier transport layer

Description

TECHNICAL FIELD [0001] The present invention relates to an anthracene compound substituted with an aryl group, a process for producing the same, and an organic thin film transistor using the same. BACKGROUND ART [0002]

The present invention relates to an anthracene compound substituted with an aryl group, a process for producing the same, and an organic thin film transistor using the same.

With the discovery of organic semiconducting compounds, the field of organic electronic materials has developed rapidly over the past two decades. Although a number of organic compounds exhibiting various semiconducting or electro-optical properties have been designed and developed, it has been generally accepted that organic electronic materials can not replace conventional semiconductor devices based on silicon. However, the charge transfer performance of organic molecules has been dramatically improved in a short period of time. Moreover, organic electronic materials have been widely used for a wide range of applications such as a possibility of producing a large area device using a solution process, easiness of changing a functional group capable of giving various chemical characteristics, Many studies and developments have been made based on the application of production structure.

Semiconductor organic compounds are currently being developed in such fields as organic thin film transistors (OTFTs), organic light emitting diodes (OLEDs), sensors and photovoltaic devices. Among them, organic thin film transistor (OTFT) is attracting attention as a most suitable technology for realizing a large-area and low-cost display, and the reported performance is approaching performance that is applicable to commercial mass production. Examples of the low-molecular-weight or oligomer organic semiconductor materials studied include melocyanine, phthalocyanine, perylene, pentacene, C60, and thiophenol oligomers. For example, in Lucent Technologies and 3M et al., Pentacene single crystals have been used to obtain high charge mobilities of 3.2 to 5.0 cm 2 / Vs or more (Mat. Res. Soc. Symp. .5.1-L66.5.11). CNRS of France reported relatively high charge mobility and current flicker ratios of 0.01 to 0.1 cm 2 / Vs using oligothiophene derivatives. On the other hand, it has been reported that a polymer-based OTFT device employing a polythiophene-based material has been tested to obtain a charge mobility of 0.01 to 0.02 cm 2 / Vs (WO 2000/7961, Science, 2000 , vol. 290, pp. 2132-2126). In addition, U.S. Patent No. 6,107,117 discloses a method of fabricating an OTFT device with a charge mobility of 0.01 to 0.04 cm 2 / Vs using a regio-regular polythiophene P3HT. However, the above technology is advantageous in terms of manufacturing process, cost, and mass production since it is a room temperature wet process, but it is difficult to purify the material with high purity, which causes low charge mobility and high blocking leakage current.

Conventionally, low-molecular-weight pentacene precursors and oligomeric polythiophene derivatives have been studied as organic semiconducting materials. Examples thereof include the following organic monomers and polymers such as poly-3-alkylthiophenes.

Figure 112009077601723-pat00001
,
Figure 112009077601723-pat00002
,
Figure 112009077601723-pat00003

However, low-molecular-weight pentacene precursors or pentacene derivatives are reported to exhibit high charge mobilities of 3.2 to 5.0 cm 2 / Vs or more. However, expensive vacuum deposition equipment is required in forming thin films, and it is difficult to form fine patterns , There is a problem that the cost is high and it is not suitable for the large-sized. In addition, pentacene is superior in crystallinity due to intermolecular orbital overlap, but because of its low solubility, it is impossible to carry out a solution process using pentacene at present, and there is a large variation in crystallinity when subjected to a deposition process, And the instability of the aromatic ring causes a side effect of forming a keto-type impurity, which weakens the overall stability of the device.

On the other hand, the polymeric or oligomer organic semiconductors are superior in solubility to low-molecular-weight organic materials such as pentacene and can be processed at a low cost, but their charge mobility is significantly lower than that of low-molecular organic materials. In addition, there is a disadvantage in that the uniformity is insufficient and it is difficult to make the material itself highly purified.

Therefore, in order to commercialize an organic thin film transistor, it is necessary to satisfy various factors such as excellent electrical stability, electric characteristics, and fairness (processability), and all advantages of a low molecular weight / high molecular weight organic semiconductor should be satisfied. Therefore, it is necessary to develop an organic compound for an organic thin film transistor which can form a thin film by a wet process and a high vacuum deposition process at a high temperature and has high charge mobility and low blocking leakage current.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to overcome the limitations of the prior art as described above, and it is an object of the present invention to provide a novel low molecular aromatic ring compound capable of solution process such as room temperature spin coating and having excellent electrical stability and performance, The purpose is to do.

It is another object of the present invention to provide an organic compound for an organic thin film transistor having a high charge mobility and a low blocking leakage current, which is excellent in solubility and capable of forming a thin film by a wet process at room temperature and a high vacuum deposition process.

The above object of the present invention is achieved by the following.

(1) An anthracenyl compound represented by the following formula (1):

Figure 112009077601723-pat00004

(2) An organic thin film transistor comprising the compound of Formula (1).

When the organic semiconductor compound of the present invention is used as an active layer in an organic thin film transistor, an organic thin film transistor capable of forming a thin film by a solution process and satisfying both high charge mobility and low blocking leakage current is manufactured There are advantages to be able to.

In addition, the organic thin film transistor manufactured by applying the organic semiconductor compound according to the present invention is characterized in that the organic thin film transistor according to the present invention is capable of forming an intermolecular arrangement or an intermolecular charge transfer And it has an excellent flicker ratio as well as an improvement in the mobility of holes and electrons due to the excellent crystallinity and the strong piobital superposition.

The present invention relates to an anthracenyl-based compound represented by the following formula (1)

[Chemical Formula 1]

Figure 112009077601723-pat00005

In the formula,

A 1 and A 2 are each independently an atom selected from the group consisting of carbon, silicon and germanium,

R 1 and R 2 are each independently selected from the group consisting of halogen atoms selected from the group consisting of hydrogen, fluorine, chlorine, bromine and iodine, linear, branched or cyclic C 1 -C 20 alkyl, fluorine, chlorine, bromine and iodine Branched or cyclic C 1 -C 20 alkyl, straight, branched or cyclic C 1 -C 20 alkenyl, straight, branched or cyclic C 1 -C 20 alkyl Linear, branched or cyclic C 1 -C 20 alkynyl, linear, branched or cyclic C 1 -C 20 alkyl, and linear, branched or cyclic C 1 -C 20 alkoxy, C 6 -C 10 Aryl, < / RTI >

And Ar is a C 4 -C 20 arylene group containing at least one heteroatom selected from the group consisting of oxygen, sulfur and selenium in the ring.

In the above formula (1), the A 1 moiety to which the three R 1 are bonded has a role of improving the solubility of the compound of formula (1) in a solvent.

When Ar does not contain a heteroatom, it may be a phenylene group, in which case R 2 is a 3-, 4-, 2,4-, 3,5-, 3,4,5-, or 2, As the substituent bonded to the 3,4,5,6-position, the substituent bonded at each position may be different from each other.

When Ar is an arylene group containing a heteroatom, preferred examples may be selected from the group consisting of the following structures.

Figure 112009077601723-pat00006

Preferable examples of R 1 include methyl, ethyl, isopropyl and isobutyl. Preferred examples of R 2 include halogen atoms, norman alkyls such as methyl, ethyl and hexyl, alkyls substituted with three halogen atoms, For example, trifluoromethyl can be mentioned.

The most preferred examples of the compound of formula (1) include those selected from the group consisting of the following formulas.

Figure 112009077601723-pat00007
,
Figure 112009077601723-pat00008
,

Figure 112009077601723-pat00009
,
Figure 112009077601723-pat00010
,

Figure 112009077601723-pat00011
,
Figure 112009077601723-pat00012
,

Figure 112009077601723-pat00013
,
Figure 112009077601723-pat00014
,

Figure 112009077601723-pat00015
,
Figure 112009077601723-pat00016
,

Figure 112009077601723-pat00017
And
Figure 112009077601723-pat00018
.

The present invention also relates to an organic thin film transistor including the compound of Formula 1 above.

The organic thin film transistor according to the present invention may have any form known in the field of the present invention.

For example, the organic thin film transistor may comprise a first electrode and a second electrode, and a thin film of a compound of formula (1) present between the first and second electrodes, wherein the compound is in the form of a thin film To constitute an organic active layer. The thin film may be formed by one or more methods selected from the group consisting of screen printing, printing, spin coating, dipping, vacuum deposition and ink jetting.

The organic thin film transistor according to the present invention may include a substrate 11, a gate electrode 16, a gate insulating layer 12, an organic active layer 13, and a source electrode 14 / a drain electrode 15 , Wherein the organic active layer (13) is formed of the compound of Formula (1).

The organic thin film transistor has a top-gate / top-contact, a top-gate-bottom-contact, a bottom-gate / top-contact or a bottom-gate / bottom-contact structure, The electrode and the drain electrode may be formed of a material selected from the group consisting of gold, silver, aluminum, nickel, neodymium aluminum (AlNd), molybdenum, copper and indium tin oxide (ITO).

Example

Hereinafter, the present invention will be described in detail with reference to examples. However, the examples are merely examples of the present invention, and the scope of the present invention is not limited by these examples.

Example 1: Preparation of 2,6-bis- (thiophene) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

(1) Preparation of 2,6-dibromoanthraquinone

Figure 112009077601723-pat00019

T-BuONO (1.95 g, 18.88 mmol), CH 3 CN (300 mL) and CuBr 2 (4.22 g, 18.88 mmol) were added to a 100 mL two-necked flask and heated to 65 ° C. 2,6-diaminoanthraquinone (20 g, 83.9 mmol) was added dropwise 4 times. After 6 hours the reaction was quenched with 20% HCl solution and the resulting solid was filtered. 1,4-dioxane. Yield: 24 g (80%), mp: 194 ℃, 1 H-NMR (300 MHz, CDCl3, ppm): 8.46 (d, 1H), 8.20 (d, 1H), 7.97 (m, 2H)

(2) Preparation of 2,6-di-thiophen-2-yl-4a, 9a-dihydro-anthraquinone

Figure 112009077601723-pat00020

Dibromoanthraquinone (0.3 g, 0.82 mmol) and 2-thiophenyl-boronic acid (0.26 g, 2.03 mmol) prepared in the above (1), 2M Na 2 CO 3 (10 mL), Pd (pph 3 ) 4 (3 mol%) and Aliquat 336 (2-3 drops) were placed under nitrogen atmosphere and dissolved in 15 mL of toluene. Then, the mixture was refluxed and stirred at 110 DEG C for 24 hours. After completion of the reaction, the reaction product was washed with methanol to obtain a solid product. The solid product obtained was then washed with boiling methylene chloride to give a clean solid product. (Yield: 70%).

(3) Preparation of 2,6-bis- (thiophene) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

Figure 112009077601723-pat00021

Triisopropylsilyl acetylene (1.34 mL, 6.04 mmol) was added to a 100 mL two-necked flask, n-BuLi (3.4 mL) was slowly added dropwise, and the mixture was refluxed at 60 ° C for 2 hours. Then, the reaction mixture was cooled to room temperature, and di-thiophenyl-anthraquinone (500 mg, 1.34 mmol) was added dropwise thereto, followed by reflux stirring at 60 ° C for 12 hours. Then, a solution prepared by dissolving SnCl 2 .2H 2 O (665 mg, 2.95 mmol) in 10% HCl (4 mL) was slowly added dropwise and the mixture was refluxed and stirred for 2 hours. After completion of the reaction, the organic layer was extracted with distilled water and methylene chloride and concentrated. Yield: 55%, molecular weight: theoretical value: 702.32, measured value (HRMS): 702.3198

Example 2: Preparation of 2,6-bis- (5-methyl-thiophene) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

(1) Preparation of 2,6-bis- (5-methyl-thiophen-2-yl) -4a, 9a-dihydro-anthraquinone

Figure 112009077601723-pat00022

Dibromoanthraquinone (1.0 g, 2.73 mmol) and 5-methyl-thiophenyl-boronic acid (1.2 g, 8.20 mmol) prepared in Example 1, (1) 2M Na 2 CO 3 (10 mL), Pd (pph 3 ) 4 (3 mol%) and Aliquat 336 (2-3 drops) were placed under a nitrogen atmosphere and dissolved in 15 mL of toluene. Then, the mixture was refluxed and stirred at 110 DEG C for 24 hours. After completion of the reaction, the reaction product was washed with methanol to obtain a solid product. The solid product obtained was then washed with boiling methylene chloride to give a clean solid product. (Yield: 75%)

(2) Preparation of 2,6-bis- (5-methylthiophene) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

Figure 112009077601723-pat00023

Triisopropylsilyl acetylene (1.9 mL, 8.50 mmol) was added to a 100 mL two-necked flask, n-BuLi (3.0 mL) was slowly added dropwise, and the mixture was refluxed and stirred at 60 ° C for 2 hours. Then, the reaction mixture was cooled to room temperature, 5-methyl-thiophenyl-anthraquinone (760 mg, 1.89 mmol) was added dropwise, and the mixture was refluxed at 60 DEG C for 12 hours. Then, a solution prepared by dissolving SnCl 2 .2H 2 O (935 mg, 4.15 mmol) in 10% HCl (4 mL) was slowly added dropwise and the mixture was refluxed and stirred for another 2 hours. After completion of the reaction, the organic layer was extracted with distilled water and methylene chloride and concentrated. The product was separated by silica column chromatography (hexane 100%) and then recrystallized from methylene chloride and MeOH. Molecular weight: theoretical value 730.35, measured value (HRMS) 730.3506, XRD analysis (Fig. 2a)

Example 3: Preparation of 2,6-bis- (5-hexyl-thiophene) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

(1) Preparation of 2,6-bis- (5-hexyl-thiophen-2-yl) -4a, 9a-dihydro-anthraquinone

Figure 112009077601723-pat00024

Dibromoanthraquinone (1.0 g, 2.73 mmol) prepared in Example 1 (1) and 2- (5-hexylthiophen-2-yl) -4, Dioxaborolane (2.40 g, 8.19 mmol), 2 M Na 2 CO 3 (10 mL), Pd (PPh 3 ) 4 (3 mol %) And Aliquat 336 (2 to 3 drops) were placed under a nitrogen atmosphere, and then dissolved in 15 mL of toluene. Then, the mixture was refluxed and stirred at 110 DEG C for 24 hours. After completion of the reaction, the reaction product was washed with methanol to obtain a solid product. The solid product obtained was then washed with boiling methylene chloride to give a clean solid product. (70% yield)

(2) Preparation of 2,6-bis- (5-hexyl-thiophene) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

Figure 112009077601723-pat00025

Triisopropylsilyl acetylene (1.2 mL, 5.00 mmol) was added to a 100 mL two-necked flask, n-BuLi (2.9 mL) was slowly added dropwise, and the mixture was refluxed and stirred at 60 ° C for 2 hours. The reaction mixture was then cooled to room temperature and 2,6-bis- (5-hexyl-thiophen-2-yl) -4a, 9a-dihydro-anthraquinone (470 mg, 1.09 mmol) Followed by reflux stirring at 60 DEG C for 12 hours. Then, a solution prepared by dissolving SnCl 2 .2H 2 O (573 mg, 2.54 mmol) in 10% HCl (4 mL) was slowly added dropwise and the mixture was stirred under reflux for 2 hours. After completion of the reaction, the organic layer was extracted with distilled water and methylene chloride and concentrated. The product was separated by silica column chromatography (hexane 100%) and then recrystallized from methylene chloride and MeOH. Molecular weight: theoretical value 870.51, measured value (HRMS) 870.5098, XRD analysis (Fig. 2b)

Example 4: Preparation of 2,6-bis- (bithiophene) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

(1) Preparation of 2,6-bis- [2,2 '] bithiophenyl-5-yl-4a, 9a-dihydro-anthraquinone

Figure 112009077601723-pat00026

Dibromoanthraquinone (1.0 g, 2.73 mmol) prepared in Example 1 (1) and 2- [2,2 '] bithiophenyl-5-yl-4 , 4,5,5- tetramethyl- [l, 3,2] dioxaborolane (2.39 g, 8.19 mmol), 2M Na 2 CO 3 (10 mL), Pd (pph 3) 4 (3 mol%) , Aliquat 336 (2 to 3 drops) were placed under a nitrogen atmosphere, and then dissolved in 15 mL of toluene. Then, the mixture was refluxed and stirred at 110 DEG C for 24 hours. After completion of the reaction, the reaction product was washed with methanol to obtain a solid product. The solid product obtained was then washed with boiling methylene chloride to give a clean solid product. (Yield 60%)

(2) Preparation of 2,6-bis- (bithiophene) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

Figure 112009077601723-pat00027

Triisopropylsilyl acetylene (931 μl, 4.19 mmol) was added to a 100-mL two-necked flask, and n-BuLi (2.33 mL) was slowly added dropwise thereto, followed by reflux stirring at 60 ° C for 2 hours. Then, the reaction mixture was cooled to room temperature, and di-bithiophenyl-anthraquinone (500 mg, 0.93 mmol) was added dropwise, followed by reflux stirring at 60 ° C for 12 hours. Then, a solution prepared by dissolving SnCl 2 .2H 2 O (462 mg, 2.05 mmol) in 10% HCl (4 mL) was slowly added dropwise and the mixture was refluxed and stirred for 2 hours. After completion of the reaction, the organic layer was extracted with distilled water and methylene chloride and concentrated. The product was separated by silica column chromatography (hexane 100%) and then recrystallized from methylene chloride and MeOH. Yield: 400 mg (50%), molecular weight: theoretical value 866.30, measured value (HRMS) 866.2998

Example 5: Preparation of 2,6-bis- (5-hexyl-bithiophene) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

(1) Preparation of 2,6-bis- (5'-hexyl- [2,2 '] bithiophenyl-5-yl) -4a, 9a-dihydro-anthraquinone

Figure 112009077601723-pat00028

Dibromoanthraquinone (1.0 g, 2.73 mmol) prepared in Example 1 (1) and 2- (5'-hexyl- [2,2 '] bithiophenyl (3.08 g, 8.19 mmol), 2M Na 2 CO 3 (10 mL), Pd (pph 3) ) 4 (3 mol%) and Aliquat 336 (2 to 3 drops) were placed under a nitrogen atmosphere, and then dissolved in 15 mL of toluene. Then, the mixture was refluxed and stirred at 110 DEG C for 24 hours. After completion of the reaction, the reaction product was washed with methanol to obtain a solid product. The solid product obtained was then washed with boiling methylene chloride to give a clean solid product. (Yield: 55%)

(2) Preparation of 2,6-bis- (5-hexyl-bithiophene) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

Figure 112009077601723-pat00029

Triisopropylsilyl acetylene (1.8 mL, 8.13 mmol) was added to a 100 mL two-necked flask, n-BuLi (2.9 mL) was slowly added dropwise, and the mixture was refluxed and stirred at 60 ° C for 2 hours. The reaction mixture was then cooled to room temperature and a solution of 2,6-bis- (5'-hexyl- [2,2 '] bithiophenyl-5-yl) -4a, 9a-dihydro-anthraquinone , 0.93 mmol) was added dropwise and the mixture was refluxed and stirred at 60 DEG C for 12 hours. Then, a solution prepared by dissolving SnCl 2 .2H 2 O (894 mg, 3.97 mmol) in 10% HCl (4 mL) was slowly added dropwise, followed by reflux stirring for 2 hours. After completion of the reaction, the organic layer was extracted with distilled water and methylene chloride and concentrated. The product was separated by silica column chromatography (hexane 100%) and then recrystallized from methylene chloride and MeOH. Molecular weight: theoretical value 1034.48, measured value (HRMS) 1034.4801, XRD analysis (FIG. 2C)

Example 6: Preparation of 2,6-bis- (benzo-bithiophene) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

(1) Preparation of 2,6-bis-benzo [b] thiophen-2-yl-anthraquinone

Figure 112009077601723-pat00030

Dibromoanthraquinone (1.0 g, 2.73 mmol) prepared in Example 1 (1), benzothiophene boronic acid (1.46 g, 8.19 mmol), 2M Na 2 CO 3 (10 mL), Pd (pph 3 ) 4 (3 mol%) and Aliquat 336 (2 to 3 drops) were placed under nitrogen atmosphere and dissolved in 15 mL of toluene. Then, the mixture was refluxed and stirred at 110 DEG C for 24 hours. After completion of the reaction, the reaction product was washed with methanol to obtain a solid product. The solid product obtained was then washed with boiling methylene chloride to give a clean solid product. (Yield: 40%)

(2) Preparation of 2,6-bis- (benzo-bithiophene) -9,10-bis- [(triisopropylsilanyl) -ethynyl] -anthracene

Figure 112009077601723-pat00031

Triisopropylsilyl acetylene (1.5 mL, 6.58 mmol) was added to a 100 mL two-necked flask, n-BuLi (2.4 mL) was slowly added dropwise, and the mixture was refluxed and stirred at 60 ° C for 2 hours. Then, the reaction mixture was cooled to room temperature, and benzothiophenyl-anthraquinone (694 mg, 1.46 mmol) was added dropwise, followed by reflux stirring at 60 캜 for 12 hours. Then, a solution prepared by dissolving SnCl 2 .2H 2 O (724 mg, 3.22 mmol) in 10% HCl (4 mL) was slowly added dropwise and then refluxed with stirring for 2 hours. After completion of the reaction, the organic layer was extracted with distilled water and methylene chloride and concentrated. The product was separated by silica column chromatography (hexane 100%) and then recrystallized from methylene chloride and MeOH. Yield: 400 mg (34%), MW: theoretical value 802.35, measured value (HRMS) 802.3466

Example 7: Preparation of 2,6-bis- (4-fluoro-phenyl) -9,10-bis - [(triisopropylsilanyl) -ethynyl]

(1) Preparation of 2,6-bis- (4-fluoro-phenyl) -4a, 9a-dihydro-anthraquinone

Figure 112009077601723-pat00032

Dibromoanthraquinone (0.4 g, 1.09 mmol), 4-fluoro-phenyl-boronic acid (0.35 g, 2.50 mmol) prepared in Example 1, (1) 2M Na 2 CO 3 (10 mL), Pd (pph 3 ) 4 (3 mol%) and Aliquat 336 (2-3 drops) were placed under a nitrogen atmosphere and dissolved in 15 mL of toluene. Then, the mixture was refluxed and stirred at 110 DEG C for 24 hours. After completion of the reaction, the reaction product was washed with methanol to obtain a solid product. The solid product obtained was then washed with boiling methylene chloride to give a clean solid product. (Yield: 80%)

(2) Preparation of 2,6-bis- (4-fluoro-phenyl) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

Figure 112009077601723-pat00033

Triisopropylsilyl acetylene (1.26 mL, 5.68 mmol) was added to a 100 mL two-necked flask, n-BuLi (3.2 mL) was slowly added dropwise, and the mixture was refluxed at 60 ° C for 2 hours. Then, the reaction mixture was cooled to room temperature, and fluorophenyl-anthraquinone (399 mg, 1.00 mmol) was added dropwise, followed by reflux stirring at 60 ° C for 12 hours. Then, a solution prepared by dissolving SnCl 2 .2H 2 O (625 mg, 2.77 mmol) in 10% HCl (4 mL) was slowly added dropwise and the mixture was refluxed and stirred for 2 hours. After completion of the reaction, the organic layer was extracted with distilled water and methylene chloride and concentrated. The product was separated by a short silica column (100% hexane) and then recrystallized with methylene chloride and MeOH. X-ray crystallization state (Fig. 6A) was determined by measuring the molecular weight of the compound of formula (I): 405 mg (55%), molecular weight: 726.39, measured value (HRMS)

Example 8: Preparation of 2,6-bis- (2,4-difluoro-phenyl) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

(1) Preparation of 2,6-bis- (2,4-difluoro-phenyl) -4a, 9a-dihydro-anthraquinone

Figure 112009077601723-pat00034

(2) was obtained in the same manner as in (1) of Example 7 except that 2,6-dibromoanthraquinone (0.4 g, 1.09 mmol) and 4-difluoro-phenyl- , 6-bis- (2,4-difluoro-phenyl) -4a, 9a-dihydro-anthraquinone was prepared to give a clean solid product. (Yield: 65%)

(2) Preparation of 2,6-bis- (2,4-difluoro-phenyl) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

Figure 112009077601723-pat00035

Triisopropylsilyl acetylene (1.2 mL, 5.00 mmol) was added to a 100 mL two-necked flask, n-BuLi (2.9 mL) was slowly added dropwise, and the mixture was refluxed and stirred at 60 ° C for 2 hours. Then, the reaction mixture was cooled to room temperature, 2,4-difluorophenyl-anthraquinone (389 mg, 0.90 mmol) was added dropwise, and the mixture was refluxed and stirred at 60 DEG C for 12 hours. Then, a solution prepared by dissolving SnCl 2 .2H 2 O (573 mg, 2.54 mmol) in 10% HCl (4 mL) was slowly added dropwise and the mixture was stirred under reflux for 2 hours. After completion of the reaction, the organic layer was extracted with distilled water and methylene chloride and concentrated. The product was separated by silica column chromatography (hexane 100%) and then recrystallized from methylene chloride and MeOH. The molecular weight of the compound was determined to be 762.37, the measured value (HRMS) of 762.3658, the X-ray crystallization state (Fig. 6b)

Example 9: Synthesis of 2,6-bis- (3,5-difluoro-phenyl) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

(1) Preparation of 2,6-bis- (3,5-difluoro-phenyl) -4a, 9a-dihydro-anthraquinone

Figure 112009077601723-pat00036

(1) of Example 7 was obtained by using 2,6-dibromoanthraquinone (0.4 g, 1.09 mmol) and 3,5-difluoro-phenyl-boronic acid (0.35 g, 2.53 mmol) 2,6-bis- (3,5-difluoro-phenyl) -4a, 9a-dihydro-anthraquinone was prepared to give a clean solid product. (Yield: 55%)

(2) Preparation of 2,6-bis- (3,5-difluoro-phenyl) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

Figure 112009077601723-pat00037

Triisopropylsilyl acetylene (1.2 mL, 5.00 mmol) was added to a 100 mL two-necked flask, n-BuLi (2.9 mL) was slowly added dropwise, and the mixture was refluxed and stirred at 60 ° C for 2 hours. Then, the reaction mixture was cooled to room temperature, 3,5-difluorophenyl-anthraquinone (470 mg, 1.09 mmol) was added dropwise, and the mixture was refluxed at 60 ° C for 12 hours. Then, a solution prepared by dissolving SnCl 2 .2H 2 O (573 mg, 2.54 mmol) in 10% HCl (4 mL) was slowly added dropwise and the mixture was stirred under reflux for 2 hours. After completion of the reaction, the organic layer was extracted with distilled water and methylene chloride and concentrated. The product was separated by silica column chromatography (hexane 100%) and then recrystallized from methylene chloride and MeOH. X-ray crystallization state (Fig. 6c) was determined by the following procedure.

Example 10: Synthesis of 2,6-bis- (4-trifluoromethyl-phenyl) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

(1) Preparation of 2,6-bis- (4-trifluoromethyl-phenyl) -4a, 9a-dihydro-anthraquinone

Figure 112009077601723-pat00038

Using the same procedure as in Example 7 (1) except that 2,6-dibromoanthraquinone (1.0 g, 2.73 mmol) and 4-trifluoromethyl-phenyl-boronic acid (1.52 g, 8.00 mmol) 2,6-Bis- (4-trifluoromethyl-phenyl) -4a, 9a-dihydro-anthraquinone was prepared to give a clean solid product. (Yield: 80%)

(2) Preparation of 2,6-bis- (4-trifluoromethyl-phenyl) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

Figure 112009077601723-pat00039

Triisopropylsilyl acetylene (1.8 mL, 8.13 mmol) was added to a 100 mL two-necked flask, n-BuLi (2.9 mL) was slowly added dropwise, and the mixture was refluxed and stirred at 60 ° C for 2 hours. Then, the reaction mixture was cooled to room temperature, and 4-trifluoromethyl-phenyl-anthraquinone (900 mg, 1.81 mmol) was added dropwise thereto, followed by reflux stirring at 60 ° C for 12 hours. Then, a solution prepared by dissolving SnCl 2 .2H 2 O (894 mg, 3.97 mmol) in 10% HCl (4 mL) was slowly added dropwise and the mixture was refluxed and stirred for another 2 hours. After completion of the reaction, the organic layer was extracted with distilled water and methylene chloride and concentrated. The product was separated by silica column chromatography (hexane 100%) and then recrystallized from methylene chloride and MeOH. Yield: 620 mg (42%), molecular weight: theoretical value: 826.38, measured value (HRMS): 826.3792

Example 11: Preparation of 2,6-bis- (3-trifluoromethyl-phenyl) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

(1) Preparation of 2,6-bis- (3-trifluoromethyl-phenyl) -4a, 9a-dihydro-anthraquinone

Figure 112009077601723-pat00040

Using the same procedure as in Example 7 (1) except that 2,6-dibromoanthraquinone (1.0 g, 2.73 mmol) and 3-trifluoromethyl-phenyl-boronic acid (1.52 g, 8.00 mmol) 2,6-Bis- (3-trifluoromethyl-phenyl) -4a, 9a-dihydro-anthraquinone was prepared to give a clean solid product. (Yield 66%)

(2) Preparation of 2,6-bis- (3-trifluoromethyl-phenyl) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

Figure 112009077601723-pat00041

Triisopropylsilyl acetylene (1.9 mL, 8.58 mmol) was added to a 100 mL two-necked flask, n-BuLi (3.0 mL) was slowly added dropwise, and the mixture was refluxed and stirred at 60 ° C for 2 hours. Then, the reaction mixture was cooled to room temperature, 4-trifluoromethyl-phenyl-anthraquinone (950 mg, 1.91 mmol) was added dropwise, and the mixture was refluxed at 60 DEG C for 12 hours. Then, a solution prepared by dissolving SnCl 2 .2H 2 O (944 mg, 4.19 mmol) in 10% HCl (4 mL) was slowly added dropwise and the mixture was refluxed and stirred for 2 hours. After completion of the reaction, the organic layer was extracted with distilled water and methylene chloride and concentrated. The product was separated by silica column chromatography (hexane 100%) and then recrystallized from methylene chloride and MeOH. Molecular weight: theoretical value: 826.38, measured value (HRMS): 826.3788

Example 12: Preparation of 2,6-bis- (3,5-trifluoromethyl-phenyl) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

(1) Preparation of 2,6-bis- (3,5-bis-trifluoromethyl-phenyl) -4a, 9a-dihydro-anthraquinone

Figure 112009077601723-pat00042

Using the same procedure as in Example 7 (1) except that 2,6-dibromoanthraquinone (1.0 g, 2.73 mmol) and 3,5-trifluoromethyl-phenyl-boronic acid (2.00 g, 8.00 mmol) 2,6-bis- (3,5-bis-trifluoromethyl-phenyl) -4a, 9a-dihydro-anthraquinone was prepared in the same manner as above to give a clean solid product. (Yield: 40%)

(2) Preparation of 2,6-bis- (3,5-trifluoromethyl-phenyl) -9,10-bis - [(triisopropylsilanyl) -ethynyl] -anthracene

Figure 112009077601723-pat00043

Triisopropylsilyl acetylene (352 μl, 1.63 mmol) was added to a 100-mL two-necked flask, n-BuLi (580 μL) was slowly added dropwise and the mixture was refluxed and stirred at 60 ° C for 2 hours. Then, the reaction mixture was cooled to room temperature, and 3,5-trifluoromethyl-phenyl-anthraquinone (230 mg, 0.36 mmol) was added dropwise thereto, followed by reflux stirring at 60 ° C for 12 hours. Then, a solution prepared by dissolving SnCl 2 .2H 2 O (180 mg, 0.80 mmol) in 10% HCl (4 mL) was slowly added dropwise and the mixture was refluxed and stirred for another 2 hours. After completion of the reaction, the organic layer was extracted with distilled water and methylene chloride and concentrated. The product was separated by silica column chromatography (hexane 100%) and then recrystallized from methylene chloride and MeOH. Yield: 90 mg (26%), molecular weight: theoretical value: 962.36, measured value (HRMS): 962.3599

Example 13: Fabrication of an organic thin film transistor

On the cleaned glass substrate, SiO 2 was formed as an insulating film by a CVD method to a thickness of 1000 Å, followed by surface cleaning, followed by drying. Subsequently, for surface treatment, the solution was immersed in an octadecyltrichlorosilane solution diluted with hexane to a concentration of 10 mM for 30 seconds, washed with acetone, and the 2 wt% chlorobenzene solution of the compound synthesized in Examples 1 to 12 was applied at 1000 rpm Lt; / RTI > Baking for 20 minutes at 70 DEG C in a glove box under an argon atmosphere and forming source and drain electrodes by vacuum deposition of gold on the organic thin film to a thickness of 500 ANGSTROM to form a top gate contact / Organic thin film transistor (OTFT) devices were fabricated. The charge mobility of the fabricated device was measured.

Further, a device including a binder polymer (organic semiconductor: polymer binder = 1: 1) was produced. The current transfer characteristics were measured using a Semiconductor Characterization System (4200-SCS) manufactured by KEITHLEY. From the saturation region current equation, we obtain a graph with (ISD) 1/2 and VG as variables and calculate the charge mobility from the slope.

Figure 112009077601723-pat00044

Where W is the channel width, L is the channel length, VG is the gate voltage, and VT is the threshold voltage. In the above equation, ISD denotes the source-drain current, μ or μFET denotes the charge mobility, C0 denotes the oxide film capacitance, W denotes the channel width, The blocking leakage current (Ioff) is the current flowing when the off state is obtained, and the minimum current is obtained from the off state in the current ratio.

Table 1 below summarizes the performance test results of organic thin film transistors fabricated using the compounds of Examples 1 to 6 as active layers.

Figure 112009077601723-pat00045

As described in the manufacturing process of the device, the compounds of Examples 1 to 6 of the present invention can be formed into an organic active layer of an organic thin film transistor through a soluble process, 2 shows that the compounds of Examples 2, 3 and 5 of the present invention have a high degree of charge mobility (blocking leakage current) when the compound is used as an organic active layer, .

Table 2 below summarizes the performance test results of organic thin film transistors fabricated using the compounds of Examples 7 to 12 as active layers.

Figure 112009077601723-pat00046

As described in the manufacturing process of the device, the compounds of Examples 7 to 12 of the present invention can be formed into an organic active layer of an organic thin film transistor through a soluble process, and Table 2 shows the compound of Example 7 Shows a high charge mobility when used as an organic active layer and shows excellent blinking ratio (blocking leakage current). FIGS. 4 and 6 show that the compounds of Examples 7 to 9 of the present invention have excellent crystallinity Show.

Therefore, the organic thin film transistor according to the present invention can have excellent electrical characteristics, and the organic active layer can be formed by a dissolvable process, so that the manufacturing cost can be reduced.

1A to 1D are cross-sectional views illustrating the structure of a general organic thin film transistor fabricated from a substrate / gate / insulating layer / source / drain / semiconductor layer.

Figs. 2A to 2C are diagrams showing the results of XRD analysis of the compounds synthesized in Examples 2, 3 and 5. Fig.

Figs. 3A to 3C are diagrams showing a differential thermal calorimetric curve of the compound synthesized in Examples 2, 3 and 5. Fig.

4A to 4C are diagrams showing the results of XRD analysis of the compounds synthesized in Examples 7 to 9.

5A to 5F are diagrams showing a differential thermal calorimetric curve of the compound synthesized in Examples 7 to 12.

6A to 6C are diagrams showing X-ray crystal states of the compounds synthesized in Examples 7 to 9. FIG.

[Description of Drawings]

11: substrate 12: gate insulating layer

13: organic active layer 14 and 15: drain electrode

16: gate electrode

Claims (12)

  1. Anthracenyl compounds selected from the group consisting of those represented by the following formulas:
    Figure 112017001636020-pat00053
    ,
    Figure 112017001636020-pat00054
    ,
    Figure 112017001636020-pat00055
    ,
    Figure 112017001636020-pat00056
    ,
    Figure 112017001636020-pat00057
    ,
    Figure 112017001636020-pat00058
    ,
    Figure 112017001636020-pat00059
    And
    Figure 112017001636020-pat00060
    .
  2. An organic thin film transistor comprising the compound according to claim 1.
  3. The organic thin film transistor according to claim 2, comprising a source electrode and a drain electrode, and a thin film of the compound existing between the source electrode and the drain electrode.
  4. The organic thin film transistor according to claim 2, wherein the compound constitutes an organic active layer.
  5. The organic thin film transistor according to claim 2, wherein the thin film is formed by at least one method selected from the group consisting of screen printing, printing, spin coating, dipping, vacuum deposition and ink jetting.
  6. 4. The organic thin film transistor of claim 3, having a top-gate / top-contact, a top-gate-bottom-contact, a bottom-gate / top-contact or a bottom-gate / bottom-contact structure.
  7. The method of claim 6, wherein the gate electrode, the source electrode, and the drain electrode are selected from the group consisting of gold, silver, aluminum, nickel, chromium aluminum neodymium (AlNd), molybdenum, copper and indium tin oxide Wherein the organic thin film transistor is formed of a material.
  8. delete
  9. delete
  10. delete
  11. delete
  12. delete
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007088115A (en) 2005-09-21 2007-04-05 Konica Minolta Holdings Inc Organic semiconductor material, organic semiconductor film, organic semiconductor device, and organic thin-film transistor
US20080210933A1 (en) 2004-11-02 2008-09-04 Hong Meng Substituted anthracenes and electronic devices containing the substituted anthracenes
WO2009079150A1 (en) * 2007-12-17 2009-06-25 3M Innovative Properties Company Solution processable organic semiconductors based on anthracene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080210933A1 (en) 2004-11-02 2008-09-04 Hong Meng Substituted anthracenes and electronic devices containing the substituted anthracenes
JP2007088115A (en) 2005-09-21 2007-04-05 Konica Minolta Holdings Inc Organic semiconductor material, organic semiconductor film, organic semiconductor device, and organic thin-film transistor
WO2009079150A1 (en) * 2007-12-17 2009-06-25 3M Innovative Properties Company Solution processable organic semiconductors based on anthracene

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